CHAPTER 1: CRYSTAL STRUCTURE

The majority of commonly used materials are in the solid state. Materials may be broadly classified as: Metals and alloys Ceramics, and Polymers Depending on the regularity with which the atoms or molecules are arranged in solids, they may be broadly classified as: Crystalline (crystal or polycrystalline form) Non-crystalline (amorphous)
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SOLID MATERIALS
CRYSTALLINE POLYCRYSTALLINE AMORPHOUS
(Non-crystalline)

Single Crystal

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CHAPTER 1: CRYSTAL STRUCTURE

Why crystalline solids? The important electronic properties of solids are best expressed in crystals. Thus the properties of the most important semiconductors depend on the crystalline structure of the host, essentially because electrons have short wavelength components that respond dramatically to the regular periodic atomic order of the specimen.

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Crystalline material is one in which the atoms are situated in a repeating or periodic array over large atomic distances.

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Single crystal: the regular periodic arrangement of atoms extends over the entire volume of solids i.e. it possesses long range order.

Polycrystalline solid: made up of an aggregate of a large number of tiny single crystals oriented in different directions and separated by well-defined boundaries

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Amorphous materials: have no regular arrangement of atoms or molecules. However, the arrangement is not completely disordered; i.e. short-ranged order of about 11.5 nm

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Lattice Translation Vectors

The geometrical arrangement of atoms in an ideal crystal (one that extends to infinity) can be described using 2 elements a lattice and a basis. Crystal Structure = Lattice + Basis

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Crystal Lattice
An infinite array of points in space, Each point has identical surroundings to all others. Arrays are arranged exactly in a periodic manner.

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Basis
The atom or group of atoms or molecules attached to each lattice point in order generate the crystal structure.

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Lattice Translation Vectors

Lattice

Basis

Crystal Structure

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Lattice Translation Vectors

The lattice is defined by three fundamental translation vectors

a1 , a2 and a3 If r defines the vector ending on one lattice point,

then the points

r ' r u1a1 u 2 a2 u3 a3

(1)

defines all the points on the lattice, where the ui are integers. A key feature is that all the points are identical i.e. the lattice appears identical when views from the point r or as when viewed from the point r '
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 r ' r 3a1 1a2 r ' 5a1 3a2

B

r
a2 a1

r'

If an observer at any point A is translated to any point B, he will not be able to detect any change in the environment i.e. the environment of all the points in a given lattice are identical.

The set of points

r ' defined by (1) for all u1, u2, u3 defines the lattice

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THE BASIS
For one basis, there is at least one atom but for complicated crystal e.g. organic proteins, there can be thousands of atoms per basis. The position of the centre of an atom j of the basis relative to the associated lattice point is

r j x j a1 y j a 2 z j a3

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Primitive Lattice Cell

The paralellepiped defined by primitive axes a1 ,a 2 and a 3 is called a primitive cell or a unit cell. The unit cell is a fundamental block which, when repeated in the three directions, will generate the entire lattice. A primitive unit cell is a minimum volume cell such that there is no cell of smaller volume that can be used as a building block for crystal structures
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Primitive Lattice Cell

There are many ways of choosing the primitive axes and primitive cell for a given lattice. The number of atom in a primitive cell or primitive basis is always the same for a given crystal structure. There is always one lattice point per primitive cell Cell volume is given as Vc a1 a2 a3

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Primitive Lattice Cell

A, B, and C are primitive unit cells. The volumes of A, B, and C are the same. The choice of origin is different, but it doesnt matter. There is only one lattice point in the primitive unit cells. D, E, and F are not. Why?

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Wigner-Seitz cells
A simple way to find the primitive cell which is called Wigner-Seitz cell can be done as follows; 1. Choose a lattice point. 2. Draw lines to connect these lattice point to its neighbours. 3. At the mid-point and normal to these lines draw new lines. 4. The volume enclosed is called as a Wigner-Seitz cell.

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Symmetry in Crystals
There are several ways in which an object may be repeated in space. These are called symmetry operations.
Symmetry operation Symmetry element

Translation
Rotation reflection Inversion

Displacement
Rotation axis Mirror plane Inversion point (or symmetry center)

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Translation
S S S S S S S

S
S

S
S

S
S S

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Rotation
90

120

180

This is an axis such that, if the cell is rotated around it through some angles, the cell remains invariant.
The axis is called n-fold if the angle of rotation is 2/n.

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Axis of rotation

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Axis of rotation

How about 5-fold symmetry?

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5-fold symmetry

Empty space not allowed

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Reflection

A plane in a cell such that, when a mirror reflection in this plane is performed, the cell remains invariant.

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Inversion Center
A center of symmetry: A point at the center of the molecule. (x,y,z) --> (-x,-y,-z) Center of inversion can only be in a molecule. It is not necessary to have an atom in the center (benzene, ethane). Tetrahedral, triangles, pentagons don't have a center of inversion symmetry. All Bravais lattices are inversion symmetric.

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Two-Dimensional Lattice Types

Mathematicians discovered that you can only fill space by using rotations of unit cells by 2, 2/2, 2/3, 2/4, and 2/6 radians (or, by 360o, 180o, 120o, 90o, and 600) But, rotations of the kind 2/5 or 2/7 do not fill space! In 2D, there are only 5 distinct lattices. These are defined by how you can rotate the cell contents (and get the same cell back), and if there are any mirror planes within the cell. From now on, we will call these distinct lattice types Bravais lattices. Unit cells made of these 5 types in 2D can fill space. All other ones cannot.
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Two-Dimensional Lattice Types

a2
a1

oblique lattice
a1 a2 , =arbitrary

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Two-Dimensional Lattice Types

a2

a1

a1

a2

Square lattice a1 = a2 , =90o

Hexagonal lattice a1 =a2 , =120o

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Two-Dimensional Lattice Types

a1

a2

a1

a1

a2

a2
Oblique

Rectangular lattice a1 a2 , =90o

a1 a2 Centered rectangular lattice a1 a2 , =90o

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Summary of Lecture 1
Crystalline Atoms are arranged in a periodic array Crystals consists of a infinite repetition of individual structural units arranged periodically in space All crystal structures can be described in terms of a lattice, with an identical group of atoms (or molecules) attached to every lattice point called the basis The lattice is formally known as a Bravais Lattice
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Summary of Lecture 1
A key feature of a Bravais lattice is that all points are identical Lattice + basis = crystal crystal structure Primitive Lattice Cell the parallelpiped difined by the primitive translation vectors defines a primitive cell or primitive unit cell. It is a minimum volume cell. It contains one lattice point per primitive cell Conventional Unit Cell a non-primitive cell that displays the symmetry of the Bravais lattice and fills all space when translated by a subset of Bravais lattice translation vectors , T
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3D-Unit cell

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